2-(3,5-Dimethyl-pyrazol-1-yl)-4-fluoro-phenylamine | 223594-48-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑类
• 英文名称: 2-(3,5-Dimethyl-pyrazol-1-yl)-4-fluoro-phenylamine
• 英文别名: 2-(3,5-Dimethylpyrazol-1-yl)-4-fluoroaniline
• CAS: 223594-48-7
• 化学式: C₁₁H₁₂FN₃
• 分子量: 205.235
• InChiKey: OEBLDYCCKMNXFK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  15
• 可旋转键数：
  1
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  43.8
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  2-(3,5-Dimethyl-pyrazol-1-yl)-4-fluoro-phenylamine 在 tetrafluoroboric acid 、 sodium azide 作用下， 以 乙醇 、 溶剂黄146 为溶剂， 反应 0.13h， 生成 8-fluoro-3-methyl-8-pyrazolo<1,2-a>quinoxaline
  参考文献：
  名称：

  Photodecomposition of Some Para-Substituted 2-Pyrazolylphenyl Azides. Substituents Affect the Phenylnitrene S−T Gap More Than the Barrier to Ring Expansion

  摘要：

  A series of para-substituted (H, Me, Cl, F, CF3, OMe, NMe2) phenyl azides bearing a dimethylpyrazolyl group in position 2 allowing intramolecular trapping of singlet nitrene have been photolyzed at both 295 and 90 K in ethanol. For three significant models (H, CF3, NMe2), the reaction has been further studied in the presence of diethylamine (DEA) and of oxygen. With all substituents but NMe2, singlet nitrene (trapped intramolecularly to give pyrazolobenzotriazoles) and didehydroazepine (trapped with DEA to give 5H-azepines and then rearranging to 3H-azepines) are in equilibrium. With the NMe2 derivative, the nonelectrophilic singlet is not trapped, while DEA adds to the benzoazirine, the precursor of the didehydroazepine. Thus, electronic effects do not hinder the equilibrium between singlet nitrene and its cyclic isomers, while determining which of the above intermediates decays to a stable end product. The electron-donating group NMe2 has a second important effect, causing a drastic enhancement of the triplet nitrene energy and reduction of the S-T gap, so that triplet nitrene is also in equilibrium with the singlet and the benzoazirine. As for triplet nitrenes,these have been characterized in matrix at 90 K, and the competition between dimerization (to give;azo compounds, as typical of such stabilized species) and hydrogen abstraction from the solvent (involving a sizable barrier) has been studied. The energetic p-dimethylamino triplet undergoes hydrogen abstraction exclusively. When present, oxygen adds efficiently to all of the nitrenes, giving a nitroso oxide, Likewise characterized in the matrix, which then converts to the nitroso and nitro,derivatives in good yields. Photochemical excitation of the triplet in matrix leads to intramolecular hydrogen abstraction.

  DOI：

  10.1021/ja982585r
• 作为产物：
  描述：

  1-<2-azido-5-(fluorophenyl)>-3,5-dimethylpyrazole 以 乙醇 为溶剂， 反应 0.13h， 生成 8-fluoro-3-methyl-8-pyrazolo<1,2-a>quinoxaline 、 8-Fluoro-2-methyl-4,5-dihydro-pyrazolo[1,5-a]quinoxaline 、 2-(3,5-Dimethyl-pyrazol-1-yl)-4-fluoro-phenylamine 、 2,2'-bis<1-(3,5-dimethylpyrazolyl)>-4,4'-difluoroazobenzene
  参考文献：
  名称：

  Photodecomposition of Some Para-Substituted 2-Pyrazolylphenyl Azides. Substituents Affect the Phenylnitrene S−T Gap More Than the Barrier to Ring Expansion

  摘要：

  A series of para-substituted (H, Me, Cl, F, CF3, OMe, NMe2) phenyl azides bearing a dimethylpyrazolyl group in position 2 allowing intramolecular trapping of singlet nitrene have been photolyzed at both 295 and 90 K in ethanol. For three significant models (H, CF3, NMe2), the reaction has been further studied in the presence of diethylamine (DEA) and of oxygen. With all substituents but NMe2, singlet nitrene (trapped intramolecularly to give pyrazolobenzotriazoles) and didehydroazepine (trapped with DEA to give 5H-azepines and then rearranging to 3H-azepines) are in equilibrium. With the NMe2 derivative, the nonelectrophilic singlet is not trapped, while DEA adds to the benzoazirine, the precursor of the didehydroazepine. Thus, electronic effects do not hinder the equilibrium between singlet nitrene and its cyclic isomers, while determining which of the above intermediates decays to a stable end product. The electron-donating group NMe2 has a second important effect, causing a drastic enhancement of the triplet nitrene energy and reduction of the S-T gap, so that triplet nitrene is also in equilibrium with the singlet and the benzoazirine. As for triplet nitrenes,these have been characterized in matrix at 90 K, and the competition between dimerization (to give;azo compounds, as typical of such stabilized species) and hydrogen abstraction from the solvent (involving a sizable barrier) has been studied. The energetic p-dimethylamino triplet undergoes hydrogen abstraction exclusively. When present, oxygen adds efficiently to all of the nitrenes, giving a nitroso oxide, Likewise characterized in the matrix, which then converts to the nitroso and nitro,derivatives in good yields. Photochemical excitation of the triplet in matrix leads to intramolecular hydrogen abstraction.

  DOI：

  10.1021/ja982585r